Fungicidal compositions and methods of combating fungi using optionally halogenated cyanophenyl o,s-dialkyl phosphorothiolates

ABSTRACT

OPTIONALLY HALOGENATED CYANOPHENYL O,S-DIALKYL PHOSPHOROTHIOLATES, I.E. CYANOPHENYL OR HALOCYANOPHENYL O,SDIALKYL PHOSPHOROTHIOLATES WHEREIN ONE OF THE ALKYL GROUPS MAY BE CYCLOALKYL, ALKYL OF 4-6 CARBON ATOMS, A CHLORINESUBSTITUTED LOWER ALKYL GROUP OR A PHENYL GROUP AND THE OTHER ALKYL GROUP IS METHYL OR ETHYL, WHICH THIOPHOSPHATES POSSESS MICROBICIDAL, ESPECIALLY FUNGICIDAL PROPERTIES.

int. 01. A0111 9/20, 9/36 US. Cl. 424210 19 Claims ABSTRACT OF THEDISCLOSURE Optionally halogenated cyanophenyl O,S-dialkylphosphorothiolates, i.e. cyanophenyl or halocyanophenyl O,S- dialkylphosphorothiolates wherein one of the alkyl groups may be cycloalkyl,alkyl of 4-6 carbon atoms, a chlorinesubstituted lower alkyl group or aphenyl group and the other alkyl group is methyl or ethyl, whichthiolphosphates possess microbicidal, especially fungicidal properties.

This is a division of application Ser. No. 104,177 filed Jan. 5, 1971,now Pat. No. 3,742,094.

The present invention relates to and has for its objects the provisionof particular new optionally halogenated cyanophenyl O,S-dialkylphosphorothiolates, i.e. cyanophenyl or halocyanophenyl O,S-dialkylphosphorothiolates wherein one of the alkyl groups may be cycloalkyl,alkyl of 4-6 carbon atoms, a chlorine-substituted lower alkyl group or aphenyl group and the other alkyl group is methyl or ethyl, whichphosphorothiolates possess microbicidal, especially fungicidalproperties, active compositions in the form of mixtures of suchcompounds with solid and liquid dispersble carrier vehicles, and methodsfor usng such compounds in a new way especially for combatingmicroorganisms, especially fungi, with other and further objectsbecoming apparent from a study of the within specification andaccompanying examples.

The specification of Japanese Patent Publication No. 16875/ 63 disclosesthat O,S-dialkyl-O-substituted phenyl phosphorothiolates haveinsecticidal activity. However, there is nothing to lead one to expectthat the compounds might have fungicidal properties or that they mightbe useful as fungicides and bactericides.

It has now surprisingly been found that the new S-alkyl-O-alkyl-O-cyanophenyl phosphorothiolates of the general formulawherein R is an alkyl group with 4-6 carbon atoms, a cycloalkyl group,chlorine-substituted lower alkyl group or a phen- Y p,

R is an alkyl group with 1 or 2 carbon atoms, and

Y is hydrogen or halogen,

exhibit excellent fungicidal activity.

United States Patent The invention also provides a process for theproduction of a compound of the formula (I) in which a compound of thegeneral formula R 0 is reacted with a phenol derivative of the generalformula CN Q wherein R R and Y have the same meanings as in formula (I)and M is hydrogen, a metal or ammonium.

As is apparent from the general formula (I), the com pounds of thisinvention have a structure characterized in that the groups R and R areasymmetric, and they exhibit excellent fungicidal activity, though theirinsecticidal activity is inferior as compared with analgous phosphatecompound of the type disclosed in Japanese Patent Publication No.16875/63.

The compounds of this invention exhibit high activity against pathogenicfungi causing diseases of plants and are excellent in that they areeffective against fungi of a broad range. Further, these compounds havelow toxicity to warm blooded animals and possess suitable affinity withhigher plants, not being phytotoxic to higher plants at ordinaryapplication concentrations. Accordingly, the compounds of this inventioncan be used suitably as agricultural and horticultural agents forpreventing and controlling diseases of plants caused by fungi.

More specifically, the compounds of this invention can be used asfungicides for protecting plants from damage caused by Archimycetes,Phycom'ycelies, Ascomycetes, Basidiomycetes, Fungi Imperfecti and otherfungi.

The active compounds of this invention can be applied for controllingpathogenic fungi living in the above ground portions of plants,pathogenic fungi invading plants from the soil and causingtracheomycosis, seedborne pathogenic fungi and soil-infectiouspathogenic fungi.

The above-mentioned excellent characteristics enable the activecompounds of this invention to give good results when applied againstdiseases caused by those pathogenic fungi that have had to be controlledby fungicides containing heavy metals harmful to men and domesticanimals, such as arsenic and mercury. Further, they give particularlygood results in controlling pathogenic fungi and bacteria causingdiseases of rice plants. More particularly, these compounds exhibitexcellent activity against Piricularia oryzea causing blast on riceplants and Pellicularia sasakii causing sheath blight, and they may beused for controlling both these organisms simultaneously. The compoundsexhibit curative activity as well as preventive activity.

Further, the compounds of this invention exhibit good controllingefiects against fungi and bacteria which infect rice plants and otheragricultural plants as Xanthomonas oryzae causing bacterial leaf blighton rice plants, Ervinia aroideae causing bacterial soft rot on chinesecabbage, Xanthomonas citri causing canker on citrus fruits, Cochliobolusmiyabeanus causing brown spot on rice plants,

Mycosphaerella musicola causing leaf spot on bananas, Botrytis cinereacausing gray mold on strawberry and other plants, Plasmopara viticolacausing downy mildew on grapes, Glomemlla cingulata causing anthracnoseon grapes, apples and pears, Sclerotinia sclerotiorum causing stem roton vegetables, Colletotrichum lagenarium causing anthracnose on melons,Diaporthe citric causing melanose on citrus fruits, Podosphaeraleucotricha causing powdery mildew on apples, Sphaerotheca fuligineacausing powdery mildew on cucumbers, Alternaria mali causing cork spoton apples, Alternaria solani causing early blight on potatoes,Alternarz'a kikuchiana causing black spot on pears, Venturia inaequaliscausing scab on apples and Venturia pirina causing scab on pears.

As described above, the compounds of this invention exhibit excellenteffects in the control of pathogenic fungi damaging rice plants andother cultivated plants. Accordingly, the compounds of this inventionare very valuable in saving the labor needed to remove diseased plantsto prevent their infection of healthy plants.

The phosphoric acid triesters of this invention are novel compoundswhich have now been synthesized for the first time. The preparation isillustrated by the following formula scheme:

R o CN /PHal +MO-Q R28 Y (II) (III) R O\() ON n s Y (I) IV Examples of Rare n-, iso-, sec or tert-butyl or pentyl or hexyl, cyclopentyl,cyclohexyl, chloromethyl, chloroethyl, 2,2,2-trichloroethyl, 1 methyl 2chloroethyl, 1-methyl-3-chloropropyl, 1-chloro-methyl2-chloroethyl,l-methyl-Z-chloropropyl, l-methyl-3-chloropropyl and phenyl, R ispreferably n-, isoor sec-butyl, cyclohexyl, 2-chloroethyl,l-methyl-2-chloroethyl, 1-chloromethyl-2- chloroethyl or phenyl.

Y is hydrogen atom or halogen such as fluorine, chlorine, bromine andiodine. Prefer-ably, it is hydrogen, chlorine or bromine.

As examples of the phosphoric acid diester monohalides of formula (II),there may be mentioned O-n-(isoor sec-) butyl-S-methyl-, O-n-(isoorsec-) butyl-S-ethyl-, O-cyclohexyl-S-methyl (or ethyl)-,O-phenyl-S-methyl (or ethyl)-, O-(2-chloro)ethyl-S-methyl,O-(l-methyl-Z- chloro)ethyl-S-methyl or ethyl)- and O-(1-chloromethyl-2-chloro)ethyl-S-methyl (or ethyl)-thiolphosphoryl chlorides.

As examples of the phenol of formula (111) there may be mentioned2-(or)4- cyanophenol, 2-cyano-4-chlorophenol, 2-cyano-4-bromophenol and2-chloro-4-cyanophenol, and salts of these phenols with ammonium or ametal such as sodium or potassium.

The reaction is preferably carried out in the presence of a solventwhich term includes a mere diluent. Any inert solvent may be used forthis purpose. Particularly good results are attainable with the use ofaliphatic and aromatic hydrocarbons which may be chlorinated, such asmethylene chloride, di-, triand tetra-chloroethylenes, chloroform,carbon tetrachloride, benzine, benzene, chlorobenzene, toluene andxylene; ethers such as diethyland di-n-butyl ethers, diox-ane andtetrahydrofurane; low molecular weight aliphatic ketones and nitrilessuch as acetone, methylethylketone, methylisopropylketone,methylisobutylketone, acetonitrile and propionitrile; low boilingaliphatic alcohols such as methanol and isopropanol; and the like.

The reaction may be conducted in the presence of an acid binder.Compounds which are usually used as acid binder, for instancehydroxides, carbonates, bicarbonates and alcoholates of alkali metalsand tertiary organic bases, such as triethylamine, dimethylaniline andpyridine, may be used.

When the reaction is effected in the absence of an acid binder, theintended product of high purity can be also obtained in high yield byforming a salt, preferably an ammonium or alkali metal salt, of thestarting phenol in advance and then reacting the salt with thephosphoric acid diester monohalide.

The reaction of the invention may be performed over a broad temperaturerange. Generally, the reaction is carried out at temperatures rangingfrom about 20 C. to the boiling point of the reaction mixture.Preferably, the reaction is elfected at about 0-100 C. It is preferableto conduct the reaction under atmospheric pressure but it is possible tocarry out the reaction under reduced or elevated pressure.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert (i.e. plant compatible or herbicidally inert)pesticide diluents or extenders, i.e., diluents or extenders of the typeusable in conventional pesticidal formulations or compositions, e.g.conventional pesticide formulation or composition such as solutions,emulsions, suspensions, emulsifiable concentrates, spray powders,pastes, wettable powders, soluble powders, oil preparations, aerosolpreparations, dusting agents, coated particles, tablets, granules,pellets, etc. These are prepared in known manner, for instance byextending the active compounds with conventional pesticide dispersibleliquid diluent carriers and/or dispersible solid carriers optionallywith the use of carrier vehicle assistants, e.g. conventional pesticidesurfaceactive agents, including emulsifying agents and/or dispersingagents, whereby, for example, in the case where water is used asdiluent, organic solvents may be added as auxiliary solvents. Thefollowing may be chiefly considered for use as conventional carriervehicles for this purpose: inert dispersible liquid diluent carriers,including inert organic solvents, such as aromatic hydrocarbons (e.g.benzene, dimethylnaphthalene, aromatic naphthas, etc.), halogenated,especially chlorinated, aromatic hydrocarbons (e.g. chloro-benzenes,etc.), paraflins (e.g. petroleum fractions), chlorinated aliphatichydrocarbons (e.g. methylene chloride, carbon tetrachloride,chloroethylene, etc.), cyclohexane, alcohols (e.g. methanol, ethanol,propanol, butanol, etc.), amines (e.g. ethanolamine, etc.), ethers,etheralcohols (e.g. glycol monoethyl ether, etc.), ketones (e.g.acetone, methylethylketone, cyclohexanone, etc.), strongly polarsolvents such as acetonitrile, amides such as dimethyl formamide,sulfoxides (e.g. dimethyl sulfoxide, etc.); and/or water; as well asinert dispersible finely divided solid carriers, such as ground naturalminerals (e.g. kaolins, attapulgite, clays, montmorillonite, chalk, i.e.calcium carbonate, talc, kieselguhr, etc.) and ground synthetic minerals(e.g. alkali silicates, etc.); whereas the following may be chieflyconsidered for use as conventional carrier vehicle assistants, e.g.surface-active agents, for this purpose: emulsifying agents, such asnon-ionic and/or anionic emulsifying agents (e.g. polyethylene oxideesters of fatty acids, polyethylene oxide ethers of fatty alcohols,alkyl sulfonates, aryl sulfonates, etc., and especially alkylarylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/ordispersing agents, such as lignin, sulfite waste liquors, methylcellulose, etc.; as well as gaseous diluents or carriers such as Freonand other aerosol propellants which are gaseous under normal conditions.

Such active compounds may be employed alone or in the form of mixtureswith one another and/or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as acaricides, insecticides,nematocides, rodenticides, plant growth-regulating agents, or fungicides(including antibiotic substances), herbicides, bactericides, etc., aswell as fertilizers, if desired, or in the form of particular dosagepreparations for specific application made therefrom, such as solutions,emulsions, suspensions, powders, pastes, and granules which are thusready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about Q.1- 9 5% by weight,and preferably 05-90% by weight, of the mixture, whereas carriercomposition mixtures suitable for direct application or fieldapplication generally contemplate those in which the active compound ispresent in an amount substantially between about 0.0001-20%, preferably0.01- 5% by weight of the mixture. Thus, the present inventioncontemplates overall compositions which comprise mixtures of aconventional dispersible carrier vehicle such as (1) a dispersible inertfinely divided carrier solid, and/or (2) a dispersible carrier liquidsuch as an inert organic solvent and/or water preferably including a surface-active effective amount of carrier vehicle assistant, e.g. asurface-active agent, such as an emulsifying agent and/or a dispersingagent, and an amount of the active compound which is effective for thepurpose in question and which is generally between about 0.0001-95%, andpreferably 0.0195%, by weight of the mixture.

The active compounds can also be used in accordance with the well knownultra-lower volume process with good success, i.e., by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very efiective atomizing equipment in finelydivided form, e.g. average particle diameter of form 50- 100 microns, oreven less i.e. mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,generally about 15 to 1000 g. per hectare, preferably about 40 to 600 g.per hectare, are sufficient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carier vehiclescontaining from about 20 to about 95% by weight of active compound oreven the 100% active substance alone, e.g. about 20-100% by weight ofthe active compound.

In particular, the present invention contemplates methods of selectivelykilling, combating or controlling the pests, e.g. fungi, and moreparticularly, methods of killing or controlling fungi which comprisesapplying to at least one of correspondingly (a) such fungi, and (b)their habitat, i.e. the locus to be protected, a correspondinglycombative or toxic amount, i.e. fungicidally elfective amount of theparticular active compound of the invention alone or together with acarrier vehicle as noted above. The instant formulations or compositionsare applied in the usual manner, for instance by spraying, atomizing,vaporizing, scattering, dusting, watering, sprinkling, pouring,fumigating, injecting, and the like.

'It will be realized, of course, that the concentration of theparticular active compound utilized in the admixture with the carriervehicle will depend upon the intended application. Therefore, in specialcases it is possible to go above or below the aforementionedconcentration ranges.

The unexpected superiority and outstanding activity of the particularnew compounds of the present invention is illustrated without limitationby the following examples.

EXAMPLE 1 11.9 g. of Z-cyanophenol and 10.2 g. of triethylamine weredissolved in mL of benzene, and 11.7 g. of S-ethyl-O-n-butylthiolphosphoryl chloride were added dropwise to thesolution at l020 C. with stirring. The stirring was continued for 2hours at 2530 C. and for another hour at 5060 C. to complete thereaction. The reaction mixture was cooled, washed with water, 1%hydrochloric acid and 1% aqueous sodium carbonate and dried overanhydrous sodium sulfate. The benzene was removed by distillation andthen the reaction mixture was subjected to distillation under reducedpressure to yield 22 g. of S- ethyl-O-n-butyl-O-(2-cyanophenyl)phosphorothiolate of the formula:

0.115s (24) The product was characterized by boiling point of 162 C./0.3 mm. Hg and a refractive index n of 1.5211.

This compound is listed in Table 1 along with others which can beprepared by analogous methods. In that table, the compounds areidentified by the indication of the specific meanings of R R and Y andthe position of the nitrile groups and of Y in formula (I).

TABLE 1 Compound number R 12 CICHBCH- Physical properties Refractiveindex Boiling point B.P. 148-150" O./0.1 mm. Hg 13.1. 156 C./0.2 mm HgB.P. 166 C./O.25 mm. Hg

B.P. 166168 C./0.1 mm. Hg ('Im 1.5400). B.P. C./0.1 mm Hg. (nD 1.5254).(m) 1.5271).

B1 engage: *4

('nn 1.5520). (7213 1.5470). (7a) 1.5552).

B.P. C./0.25 mm. Hg (110 1.5398).

B.P. 171 C./0.1 mm. Hg (no 1.5520).

13.1. 173 C./0.15 mm. Hg (17.13 1.5463):

TABLE 1C0ntinued Physical properties d R1 R ON Y Boiling pointRefractive index 10 010H20H20H- CH1 4-0N 2-01 20 Q CH5 2-ON H B.P.177-170 0. 0.15 mm. H (7113 1.5798).

2-011 401 Br. ITS-186 0./0.15 mm. H @15 1.5878). 21 as 4-0N 11 HP. 1350. 0.0a mm. H 55 15832). 4-CN Z-Cl (1m 1.5922). 2-CN H 18.1. 162C./0.3I|11I1. Hg (ma 1.5211) 2 CN -Cl 13.1. 155158 C./0.25 mm. Hg (711.5318) 4-0N H B.P.158160 0./0.1 mm. H 115 1.5234). 4-0N 2-01 13.1.1s4-105 0. 0.15 mm. H (7111 1.5345). 2-0N H B.P. 147 0. 0.2 mm. H (111)1.5214).

N H 13.1. 147 0. 0.2 mm. H (11.5 1.5214). 3-810 H (1117 1.5241 20 ec-0H.0211. 2-011 4-01 115 15330).

31 C1115 2-CN H a (7L!)20 1.5390).

S m asabove 02H Z-CN 4-Cl (71n1.5468). kin 01H: 4-0N H (71.13" 1.5430).34 ..do C2115 4-0N 2-01 (71.11 1.5506).

: ClCHzCH- C2115 2-0N 13.1. 100-103 0./0.2 mm. H (1113 1.5357).

35 CICH2CH- 02H. 2-0N 4-01 13.1. 180 0./0.4 mm. Hg (121) 1.5480).

I CH3 37 c10H10H- 0,115 4-CN H B.P. 178 0. 0.s mm. Hg (55 1.5407

I CH1 as ClCHgCH- 01H. 4-0N 2-01 715 1.5547

I C}I3 a0 C1CH2CH- 021-15 2-0N 4-Br (115 1.5640).

I CH7 4 010H CH- 0 H. 2-0N H B.P.175 0./0.05 mm. H 11.5 1.5490). 4 1gcmHiiioH- 02H: 2-CN 4-01 1m 1.5575

42 Q C2115 2-0N H 13.1. 176 0. 0.13 mm. Hg (71)) 1.5720).

0 H 2010 4-01 13.1. 100 0./0.2 mm. H (1m 1.5790). """Tilfffiififfii 02H:4-0N H B.P. 175 0. 0.07 mm. H (11.5 1.5708). 45 .410 C2H5 4-0N 2-01 1151.5830).

EXAMPLE 2 45 EXAMPLE 5 15 parts by weight of compound (17) of Table l,80 parts by weight of diatomaceous earth and 5 parts by weight of anemulsifier (i.e. polyoxyethylene alkylaryl ether) are mixed and crushedto prepare a wettable powder. This formulation may be diluted with waterto the desired concentration and then be used as aready-to-usepreparation.

EXAMPLE 3 parts by weight of compound (7) of Table 1, 30

parts by weight of xylene, 30 parts by weight of Kawakasol (an aromatichydrocarbon with a boiling range of 150 to 200 C.) and 10 parts byweight of the emulsifier Sorp01 (i.e. polyoxyethylenealkylaryl ether)are mixed and stirred to prepare an emulsifiable concentrate (anemulsifiable liquor). This formulation may be diluted with water to thedesired concentration and then used as a ready-touse-preparation.

EXAMPLE 4 To a mixture consisting of 10 parts by Weight of compound (24)of Table 1, 10 parts by weight of bentonite, 78 parts by weight of amixture of talc and clay (1:3) and 2 parts by weight of lignin sulfate,25 parts by weight of Water are added and the mixture is firmly kneaded.It is finely cut into granules of 0.5 to 1.5 mm. diameter by means of agranulating machine. The granules are then dried at a temperaturebetween to C. to obtain a granular formulation. This formulation maydirectly be applied to the soil.

2 parts by weight of compound (27) of Table 1 and 98 parts by weight ofa mixture of talc and clay (1:3) are mixed and crushed to prepare adust. This formulation may directly be used as aready-to-use-preparation.

EXAMPLE 6 Test on Blast of Rice Plants (Pirz'cularia vryzae) Preparationof sample chemical liquor Solvent: 1 part by weight of acetoneDispersing agent: 0.05 part by weight of sodium oleate Other additive:0.2 part by weight of gelatin Water: 98.75 parts by weight Aconcentrated emulsifiable liquor (obtained by adding the active compoundin an amount sufficient to obtain the prescribed concentration to theabove amount of the solvent) was admixed with the above amount of watercontaining the above amounts of the dispersing agent and gelatin.

Test procedures (a) Test of preventive effect and the durability ofeffect (residual effect): Rice plant (jukkoku variety) was cultivated ina pot of 12 cm. diameter and the above-mentioned diluted liquorcontaining the active compound of this invention at the prescribedconcentration was applied to the rice plant in the amount of 50 ml. per4 pots.

One half of the chemical-sprayed rice plant was kept in a chambermaintained at 25 C. and a relative humidity of 100% for 2 days from thenext day after the chemical spraying and the remaining half was kept inthe same chamber for 2 days from the fourth day after the chemicalspraying. While in the chamber, the rice plant was twice inoculated byspraying with a suspension of spores of artificially cultured pathogenicfungi of blast. From the results of the infection made the next dayafter the chemical spraying, the direct preventive effect can beevaluated, and from the results of the infection made the fourth dayafter the chemical spraying, the durability of the preventive effect(residual effect) can be ascertained.

Seven days after inoculation, the degree of infestation was determinedby applying a scale ranging from to 5, and the protective value of eachparticular active compound against Piricularia oryzae was determined inaccordance with the formula below.

At the same time, the phytotoxicity against rice plants was determined.

Infested area of leaf in percent Degree of infestation: of total leafDegree of infestation of non-treated plants The active compounds testedand the average results obtained can be seen from the following Table:

TABLE 2 [Results of tests on efiects against blast oi rice plant] Activecomponent concentration Preventive .p.m. a cot Protective value ResidualPhytoetfect toxicity Compound number MW Ill I q I NI TABLE 2-ContinuedActive Protective value component Compound concentration PreventiveResidual Phytonumber (p.p.m.) effect eflect toxicity 250 100 74 500 100100 250 100 68 500 100 96 250 92 72 500 100 84 250 100 96 500 100 100250 100 78 500 100 250 92 74 500 86 250 as 75 500 98 84 250 100 76 500100 100 250 94 68 500 100 100 250 500 25o 500 250 500 250 500 250 500250 500 250 500 250 500 250 500 100 480 86 22 0 0 (Control)-.

N OTE.-

(1) The compound numbers in the Table correspond to those in Table 1 (2)Comparison is commercially available. 0,0-dllsopropyl-S-benzylphosphorothiolate.

(3) The symbol in column Phytotoxicity means that the chemical did notadversely affect the growth of the rice plant.

Rice plant (Kinmaze variety) was cultivated in a 12 cm. diameter pot,and at the primary tillering stage the diluted liquor containing theactive compound at the prescribed concentration, which was prepared inthe same manner as in Example 6, was applied to the rice plant in anamount of 50 ml. per 3 pots.

The next day, the root of the sample rice plant was inoculated withpathogenic fungi of sheath blight which had been cultured in a barleyculture medium for 10 days and in which sclerotia had been formed. Thenthe sample was kept in a chamber maintained at 28-30 C. and a relativehumidity of more than 95% for 8 days. The degree of the disease wasexamined.

The degree of infestation was determined by means of the formula (1) andthe protective value of each compound was calculated in accordance withthe formula (2):

Degree of infestation 3. N (1) wherein N=the number of the total stemsexamined n =the number of non-infested stems Plant Pathogens Test (AgarDilution Method) The active compound was mixed in an agar culture mediumof potato to form the desired concentration of active compound therein.After the medium was poured into Petri dishes of 9 cm. diameter andcoagulated, the same were inoculated with the corresponding plantpathogens. A control Petri dish to which no active compound was added,was also set up. After having been cultured at a temperature of 27 C.for 4 days, the growth condition of the plant pathogens was investigatedand the degree of illfungal growth was determined by applying a scaleranging from to 5 as follows:

The active compounds tested and the average results obtained can be seenfrom the following Table:

Degree of illfungal growth Manama- O 1 2 What is claimed is: 1. A methodof combating fungi which comprises ap plying to the fungi or a habitatthereof a fungically effective amount of an organic phosphoric ester ofthe formula R s Y (I) wherein R is an alkyl group with 4-6 carbon atoms,a cycloalkyl group, chlorine-substituted lower alkyl group or a phenygroup,

R is an alkyl group with 1 or 2 carbon atoms, and

Y is hydrogen or halogen,

Y and CN being present in the 2- and 4-positions.

2. The method according to claim 1 in which R is n-, isoor sec-butyl,cyclohexyl, 2-chloroethyl, 1-methy1-2- chloroethyl,l-methyl-3-chloropropyl, l-chloromethyl-Z- chloroethyl or phenyl, and Yis hydrogen, chlorine or bromine.

3. The method according to claim 1 wherein such compound isS-methyl-O-n-butyl-O-(2-cyanophenyl) phosphorothiolate of the formula 4.The method according to claim 1 wherein such compound isS-methyl-O-cyclohexyl-O-(2-cyanophenyl) phosphorothiolate of the formulaCN t Pallicularia aasakii (rice) Concentration of active Piriculariaingredient, oryzae p.p.m. (rice) C ompound number Untreated (control) OICOCO 060 000 COCO It will be realized by the artisan that all of theforegoing compounds contemplated by the present invention possess thedesired strong fungieidal properties, with regard to a broad spectrum ofactivity, as well as a comparatively low toxicity toward warm-bloodedcreatures and a concomitantly low phytotoxicity, enabling such compoundsto be used with correspondingly favorable compatibility withwarm-blooded creatures and plants for more effective control and/ orelimination of fungi by application of such compounds to such fungiand/or their habitat.

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

Xanthomonas oryzae (rice) r .0 UI (HOOD NUOO NON- O HUIOO Sclerotim'asclero- Collatetiorum iridium (vegelagenarimn tables) (melon)Sclerotinia cmerea (peach) Alternaria Diaporthe Glomerella kikuchianacitri cinguluta (pear) (citrus) (grape) en es -co (ammo Nil- MO cocneuooi Mencc: catch-o oucnoo octcco p on HUOO tcv-cno totoo moi-o en MHGQWhit-O tor-mo i mwc :n Hero Nut- O ammo em-oic 5. The method accordingto claim 1 wherein such compound isS-methyl-O-cyclohexyl-O-(2-cyano-4-chlorophenyl) phosphorothiolate ofthe formula CH; S (12) 13 7. The method according to claim 1 whereinsuch compound is S-methyl-O-(l-methyl-Z-chloroethyl)O-(2-cyano-4-chlorophenyl) phosphorothiolate ofthe formula CN c1cm( ;H\(

cm P-0- 1 8. The method according to claim 1 wherein such compound isS-methyl-0-(1-methyl-3-chloropropyl)O-(2-cyanophenyl) phosphorothiolateof the formula ON C1CHiCHa(l3HO\(|? CH; /PO CHa-S (1 9. The methodaccording to claim 1 wherein such compound isS-methyl-O-(l-methyl-B-chloropropyl)O-(2-cyano-4-chlorophenyl)phosphorothiolate of the formula CN ClCHaCHs?H-O\(fi CH; /PO Cl CHJ-S 7)10. The method according to claim 1 wherein such compound isS-methyl-O-phenyl-O-(Z-cyanophenyl) nhn phorothiolate of the formula ONQ o CHa-S (20) 11. The method according to claim 1 wherein such compoundis S-ethyl-O-n-butyl-O-(Z-cyanophenyl) ohmphorothiolate of the formulaCgHr-S 12. The method according to claim 1 wherein such compound isS-ethyl-O-n-butyl-O-(2-chloro-4-cyanophenyl) phosphorothiolate of theformula n- LHP 0 CQH-QS 13. The method according to claim 1 wherein suchcompound is S-ethyl-O-iso-butyl-O-(Z-cyanophenyl) phos- 14. The emthodaccording to claim 1 wherein such compound isS-ethy1-O-sec.-butyl-O-(2-cyanophenyl) phosphorothiolate of the formulaa r-B 15. The method according to claim 1 wherein such compound isS-ethyl O cyclohexyl-O-(Z-cyanophenyl) phosphorothiolate of the formula4-bromophenyl) phosphorothiolate of the formula alls-B 17. The methodaccording to claim 1 wherein such compound is S-methyl O(1-cloromethyl-Z-chloroethyl)O- (2-cyano-4-chlorophenyl)phosphorothiolate of the formula 18. The method according to claim 1wherein such compound is S-methyl-O-phenyl-G(2-cyanophenyl)phosphorothiolate of the formula fi- Q CzHs-S 19. A fungicidalcomposition comprising a fungicidally effective amount of an organicphosphoric acid ester of the formula R 0 0 CN wherein R is an alkylgroup with 4-6 carbon atoms, a cylcloalkyl group, chlorine-substitutedlower alkyl group or a phenyl group,

R is an alkyl group with 1 or 2 carbon atoms, and

Y is hydrogen or halogen,

Y and CN being present in the 2- and 4-positions.

in admixture with an inert diluent.

References Cited UNITED STATES PATENTS 3,309,371 3/1967 Curry et al.250940 ALBERT T. MEYERS, Primary Examiner A. I. ROBINSON, AssistantExaminer k1nl'l 131 blA USS lA l l'lNl OFFICE C-ER'LIFICK'DE OFCORRECTl'ON Patent: No. 3,826,831 Dated July 30, 197A lnventofls) SHIGEOKISHINO E'l AL It is certified that error appearsin the.aooye-identified patent and that said Letters Patent are herebycorrected as shown Below:

001. l, line '7, correct spelling of inventor "Knlc'ahasnzl" a Col. 2,line 4, correct Compound (11) to read as follows:

,Col. 5, line-l8, cancel "lower" and substitute low- Cols} 7 and 8,Table I, cancel "Compound 28.......1(ng l.52l2)."

second occurrence.

Col. 13, claim 12, correct the formula for Compound (27) to read" asfollows:

Col. 13, claim l l, line 1, correct spelling of "method".

Col. 14, Claim. 18, line 2, change "methyl" to ethyl Col. 14, Claim 19,line 2 after the formula, correct spelling of "cycle".

Signed and sealed this 26th day of November 1974.

(SEAL) Attest: 1 p A moor M. GIBSON JR. c. MARSHALL *DANN Commissionerof Patents Attesti'ng 1 0fficer i l 1

